Article
Formation of β-Metallanaphthalenes by the Coupling of a Benzo-Iridacyclopentadiene with Olefins
Author/s | Vivancos Ureña, Ángela
Hernández, Yohar A. Paneque Sosa, Margarita López Poveda, Manuel Salazar Pereda, Verónica Álvarez González, Eleuterio |
Department | Universidad de Sevilla. Departamento de Química Inorgánica |
Publication Date | 2015 |
Deposit Date | 2018-09-17 |
Published in |
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Abstract | We have synthesized a new type of metallaaromatic complexes, namely the hydride-β-iridanaphthalenes TpMe2tiebar above startr(H)[C(CH2R′)-C6H4-o-C(R)═tiebar above endC(R)] (benzo-3-H,CH2R′), by reaction of the benzo-irida ... We have synthesized a new type of metallaaromatic complexes, namely the hydride-β-iridanaphthalenes TpMe2tiebar above startr(H)[C(CH2R′)-C6H4-o-C(R)═tiebar above endC(R)] (benzo-3-H,CH2R′), by reaction of the benzo-iridacyclopentadiene TpMe2tiebar above startr[C6H4-o-C(R)═tiebar above endC(R)](OH2) (benzo-1-OH2) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate, R = CO2Me) with olefins of the type CH2═CHR′ (R′ = H, Me, C6H4-p-Me, OPh). These reactions are proposed to take place with the initial coordination of the olefin and isomerization to a carbene form and subsequent insertion into the Ir–C(phenylic) bond and a final α-H elimination. The reaction with ethoxyethylene does not afford the corresponding derivative but rather gives a mixture of three, isolable, compounds, which are proposed to derive from three different types of insertion of the olefin, one of them a typical 1,2-insertion and the other two as (different) carbenes. The related reactions of the iridacyclopentadiene TpMe2tiebar above startr[C(R)═C(R)-C(R)═tiebar above endC(R)](OH2) (1-OH2) are also discussed. For different combinations of precursor and olefin, we have observed differences in the regio- and stereochemistry of the insertions. |
Funding agencies | Ministerio de Ciencia e Innovación (MICIN). España Junta de Andalucía |
Project ID. | CTQ2010-17476
Consolider-Ingenio 2010 CSD2007-00006 FQM-119 P09-FQM-4832 |
Citation | Vivancos Ureña, Á., Hernández, Y.A., Paneque Sosa, M., López Poveda, M., Salazar Pereda, V. y Álvarez González, E. (2015). Formation of β-Metallanaphthalenes by the Coupling of a Benzo-Iridacyclopentadiene with Olefins. Organometallics, 34 (1), 171-188. https://doi.org/10.1021/om5010435. |
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